New Polymer Chain Architecture:  Synthesis and Characterization of Star Polymers with Comb Polystyrene Branches

Highly branched starlike comb polystyrenes (star polymers with four and five arms constituted of PS combs) have been synthesized. The strategy developed is based on the highly selective coupling reaction of living polystyryllithium onto poly(chloroethyl vinyl ether) chains with a starlike chain architecture. The PS grafts and the poly(CEVE) building blocks were prepared individually by living polymerization techniques. The solution properties and the characteristic parameters ([η], R g, R h, ρ) of these new PS comb star macromolecules were determined and compared to those of the corresponding “linear” PS combs. The results confirm the much higher compactness of the new macromolecular structures, which behave as hard spheres in the whole molar mass domain examined.